A theoretical study of the structure and bonding of UOX4 (X = F, Cl, Br, I) molecules: the importance of inverse trans influence.

During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (T(c)), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions.     

Liquid chromatographic analysis of vitamin B6 in reconstituted infant formula: collaborative study

A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials.     

Isolation,anticholinesterase properties and acute toxicity of the four stereoisomers of the nerve agent soman

Abstract

The four stereoisomers of pinacolyl methylphospho-nofluoridate (soman) were isolated with more than 99% optical purity. The bimolecular rate constants for inhibition of electric eel acetylcholinesterase and the LD₅₀-values (sc, mice) of the stereoisomers were determined.     

The high-temperature heat capacity of ThPd3 and UPd3

The enthalpy increments of UPd₃ and ThPd₃ have been measured using the drop calorimetry for temperature range (480 to 1290) K. The heat capacity curves have been derived using the simultaneous linear regression of our data and the low temperature heat capacity data from previous studies. Furthermore the Schottky contributions for UPd₃ were determined by comparing the ThPd₃ and UPd₃ heat capacity functions and correlated with the theoretical values calculated from the crystal field energy levels.     

Thermodynamic properties and phase diagrams of fluoride salts for nuclear applications

This work is a critical review of the chemical-physical properties of the fluoride salts of interest in the Molten Salt Reactor project. In total five salt compositions are discussed. Two of them are choices for coolant applications (based on LiF-BeF₂ and NaF-NaBF₄ systems) one is considered as a heat transfer salt (LiF-NaF-KF system) whereas the other two are the main candidates for the fuels in non-moderated breeder and thermal breeder reactors, respectively (LiF-ThF₄ and LiF-BeF₂-ThF₄ systems). For all the systems the phase diagrams are presented with the emphasis on the melting behaviour and the vapour pressure. Heat capacity, density, viscosity and thermal conductivity, as well as the solubility for actinides in case of the fuels are presented also.     

The low-temperature heat capacity of CaUO4 and SrUO4

The heat capacity of calcium monouranate CaUO₄ and strontium monouranate SrUO₄ have been measured over the temperature range (2 to 300) K. The results are significantly different from earlier measurements, confirming the conclusions from our previous study on BaUO₄. The standard entropy at T = 298.15 K of orthorhombic α-SrUO₄ is consistent with the values for the isostructural BaUO₄ as well as the alkali uranates Na₂UO₄ and Cs₂UO₄. The standard entropy of the rhombohedral CaUO₄ is appreciably different, which is attributed to the different structures of the uranium sublattices.     

Mean velocity profile in a sheared and thermally stratified atmospheric boundary layer

A stability correction function φ(m)(ζ) that accounts for distortions to the logarithmic mean velocity profile (MVP) in the lower atmosphere caused by thermal stratification was proposed by Monin and Obukhov in the 1950s using dimensional analysis. Its universal character was established from many field experiments. However, theories that describe the canonical shape of φ(m)(ζ) are still lacking. A previous link between the spectrum of turbulence and the MVP is expanded here to include the effects of thermal stratification on the turbulent kinetic energy dissipation rate and eddy-size anisotropy. The resulting theory provides a novel explanation for the power-law exponents and coefficients already reported for φ(m)(ζ) from numerous field experiments.     

Mass spectrometric studies of the vapour phase in the (Pu + O) system

Vapour pressure measurements at high temperatures have been performed on plutonium oxide samples using a Knudsen cell coupled with a mass spectrometer. Different experimental conditions were applied for the derivation of the solid–gas phase relations for three composition in the Pu–O phase diagram: the (Pu₂O₃–PuO_2?x) two-phase domain, the congruent vapourisation composition and near stoichiometric PuO_2.00. The partial pressures of the gaseous species PuO₂, PuO, and Pu were assessed from ionisation efficiency curves recorded at constant temperature. The vapour pressure results for different phase fields were discussed together with all the available literature data.